JP2001354709A - Surface active agent composition for emulsion polymerization - Google Patents
Surface active agent composition for emulsion polymerizationInfo
- Publication number
- JP2001354709A JP2001354709A JP2000179491A JP2000179491A JP2001354709A JP 2001354709 A JP2001354709 A JP 2001354709A JP 2000179491 A JP2000179491 A JP 2000179491A JP 2000179491 A JP2000179491 A JP 2000179491A JP 2001354709 A JP2001354709 A JP 2001354709A
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- JP
- Japan
- Prior art keywords
- emulsion polymerization
- emulsion
- polymerization
- active agent
- surface active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polymerisation Methods In General (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、水への溶解性及び
重合性能に優れ、機械的安定性及び化学的安定性が良好
なポリマーエマルションを与える乳化重合用界面活性剤
組成物、及びビニル系モノマーの乳化重合法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a surfactant composition for emulsion polymerization which provides a polymer emulsion having excellent solubility in water and polymerization performance, and excellent mechanical stability and chemical stability, and a vinyl-based surfactant composition. The present invention relates to a method for emulsion polymerization of monomers.
【０００２】[0002]
【従来の技術及び発明が解決しようとする課題】酢酸ビ
ニル、アクリル酸エステル、メタクリル酸エステル、ス
チレン、ブタジエン等のビニル系モノマーの乳化重合に
よって得られるポリマーエマルションは、水分散系のま
ま塗料、接着剤、紙加工剤、繊維加工剤等の分野に、あ
るいはポリマーが分離されてプラスチック、ゴムとして
広く工業的に使用されている。乳化重合には乳化剤とし
て、直鎖アルキル硫酸エステル塩、直鎖アルキルベンゼ
ンスルホン酸塩（ＬＡＳ）、ポリオキシエチレンアルキ
ルエーテル硫酸エステル塩、ポリオキシエチレンアルキ
ルフェニルエーテル硫酸エステル塩等の陰イオン界面活
性剤、及びポリオキシエチレンアルキルエーテル、ポリ
オキシエチレンアルキルフェニルエーテル等の非イオン
界面活性剤が、それぞれ単独に、あるいは陰イオン−非
イオン界面活性剤の混合系で用いられる。2. Description of the Related Art Polymer emulsions obtained by emulsion polymerization of vinyl monomers such as vinyl acetate, acrylic acid esters, methacrylic acid esters, styrene, butadiene, etc. can be used as paints or adhesives in a water-dispersed state. It is widely used industrially in the fields of chemicals, paper processing agents, fiber processing agents, etc., or as a plastic or rubber from which polymers have been separated. In the emulsion polymerization, anionic surfactants such as linear alkyl sulfate, linear alkyl benzene sulfonate (LAS), polyoxyethylene alkyl ether sulfate, and polyoxyethylene alkyl phenyl ether sulfate as emulsifiers; And non-ionic surfactants such as polyoxyethylene alkyl ether and polyoxyethylene alkyl phenyl ether are used alone or in a mixed system of an anionic and non-ionic surfactant.
【０００３】乳化重合における乳化剤は、重合の開始反
応、成長反応に影響を及ぼすのみでなく、重合中の機械
的安定性、化学的安定性にも大きな影響を及ぼす。特に
非イオン界面活性剤は、多価金属カチオン等に対して影
響を受けずポリマーエマルションを安定化させる性質が
あることから、化学的安定性の付与に効果的である。[0003] Emulsifiers in emulsion polymerization not only affect the initiation reaction and the growth reaction of the polymerization, but also greatly affect the mechanical stability and the chemical stability during the polymerization. In particular, nonionic surfactants are effective in imparting chemical stability because they have the property of stabilizing a polymer emulsion without being affected by polyvalent metal cations and the like.
【０００４】一方ポリマーエマルションの製造工程にお
いては、非イオン界面活性剤の使用に際し、いったんこ
れを分散媒である水に溶解することが必要である。従来
用いられてきたポリオキシエチレンノニルフェニルエー
テルやポリオキシエチレンドデシルエーテル等の非イオ
ン界面活性剤の場合、溶解の為に長時間を要したりある
いは非イオン界面活性剤を水とともに加熱する必要があ
った。特にモノマーをあらかじめ水中に乳化してプレエ
マルションをつくって、重合系に添加するプレエマルシ
ョン法による乳化重合では、加熱された高温の非イオン
界面活性剤水溶液をモノマーと混合乳化することは突発
的重合反応のおそれがあるため避けなければならない。
そのため非イオン界面活性剤を水中で加熱溶解する場合
には冷却工程も必要であった。あらかじめ希釈容易な10
〜20重量％の非イオン界面活性剤水溶液を調製してお
き、必要量を添加する手段もあるが、これもまた別の貯
蔵タンクを要する欠点がある。On the other hand, in the production process of a polymer emulsion, when using a nonionic surfactant, it is necessary to once dissolve it in water as a dispersion medium. In the case of nonionic surfactants such as polyoxyethylene nonylphenyl ether and polyoxyethylene dodecyl ether which have been conventionally used, it takes a long time to dissolve or it is necessary to heat the nonionic surfactant together with water. there were. In particular, in emulsion polymerization by the pre-emulsion method in which a monomer is emulsified in water in advance and added to the polymerization system, mixing and emulsification of a heated, high-temperature nonionic surfactant aqueous solution with the monomer is a sudden polymerization. It must be avoided because of the risk of reaction.
Therefore, when heating and dissolving the nonionic surfactant in water, a cooling step is also required. 10 easy to dilute in advance
Although there is a means for preparing an aqueous solution of a nonionic surfactant of -20% by weight and adding a necessary amount, this also has a disadvantage that a separate storage tank is required.
【０００５】本発明の課題は、水への溶解が常温でも容
易で、かつモノマー乳化性に優れ、重合後のポリマーエ
マルションの化学的安定性も良好な乳化重合用界面活性
剤組成物、及びビニル系モノマーの乳化重合法を提供す
ることにある。An object of the present invention is to provide a surfactant composition for emulsion polymerization which is easy to dissolve in water even at room temperature, has excellent monomer emulsifiability, and has a good chemical stability of a polymer emulsion after polymerization. An object of the present invention is to provide an emulsion polymerization method for a system monomer.
【０００６】[0006]
【課題を解決するための手段】本発明は、式（Ｉ）で表
される化合物を含有し、その含有量が、非イオン界面活
性剤成分の50重量％以上である乳化重合用界面活性剤組
成物、及びこの乳化重合用界面活性剤組成物を用いるビ
ニル系モノマーの乳化重合法である。According to the present invention, there is provided a surfactant for emulsion polymerization containing a compound represented by the formula (I), the content of which is 50% by weight or more of the nonionic surfactant component. A composition and an emulsion polymerization method of a vinyl monomer using the surfactant composition for emulsion polymerization.
【０００７】[0007]
【化２】 Embedded image
【０００８】（式中、x，yはそれぞれ０以上の整数で、
x＋y＝８である。EOはオキシエチレン基を示し、nはオ
キシエチレン基の平均付加モル数を示す５〜100の数で
ある。）(Where x and y are each an integer of 0 or more,
x + y = 8. EO represents an oxyethylene group, and n is a number of 5 to 100 representing the average number of added moles of the oxyethylene group. )
【０００９】[0009]
【発明の実施の形態】式（Ｉ）において、x、yはそれぞ
れ０以上の整数で、x＋y＝８であるが、yは０〜２が好
ましく、特に０又は１が好ましい。nは、重合安定性、
化学的安定性の観点から、５〜100の数であるが、好ま
しくは10〜50、特に好ましくは15〜40である。BEST MODE FOR CARRYING OUT THE INVENTION In the formula (I), x and y are each an integer of 0 or more and x + y = 8, and y is preferably 0 to 2, and particularly preferably 0 or 1. n is polymerization stability,
From the viewpoint of chemical stability, the number is 5 to 100, preferably 10 to 50, particularly preferably 15 to 40.
【００１０】式（Ｉ）の化合物は、ｎ−ウンデシルアル
コール、２−メチルデシルアルコール、１−デセンのオ
キソ反応で得られる炭素数１１のオキソアルコール（主
としてyが０又は１の化合物の混合物）等に、エチレン
オキサイドを付加することにより得ることができる。The compound of the formula (I) is an oxo alcohol having 11 carbon atoms obtained by an oxo reaction of n-undecyl alcohol, 2-methyldecyl alcohol and 1-decene (mainly a mixture of compounds in which y is 0 or 1). And the like can be obtained by adding ethylene oxide.
【００１１】式（Ｉ）の化合物の含有量は、水への溶解
性の観点から、本発明組成物中の非イオン界面活性剤成
分の50重量％以上であることが必要であり、好ましくは
75重量％以上、特に好ましくは90重量％以上である。ま
た本発明の乳化重合用界面活性剤組成物中の非イオン界
面活性剤の含有量は、化学的安定性の観点から、30〜85
重量％が好ましく、50〜80重量％が更に好ましい。The content of the compound of the formula (I) must be at least 50% by weight of the nonionic surfactant component in the composition of the present invention from the viewpoint of solubility in water.
It is at least 75% by weight, particularly preferably at least 90% by weight. The content of the nonionic surfactant in the surfactant composition for emulsion polymerization of the present invention, from the viewpoint of chemical stability, 30 to 85.
% By weight, more preferably 50-80% by weight.
【００１２】本発明の界面活性剤組成物中に非イオン界
面活性剤成分として、式（Ｉ）で表される化合物以外の
非イオン界面活性剤を併用する場合には、従来より使用
されてきた非イオン界面活性剤、例えばポリオキシエチ
レンノニルフェニルエーテル、ポリオキシエチレンドデ
シルエーテル、炭素数12〜15のオキソアルコールのエト
キシレート、ポリオキシエチレンオレイルエーテル、モ
ノ又はジスチレン化フェノールのエトキシレート等を用
いることができる。When a nonionic surfactant other than the compound represented by the formula (I) is used as a nonionic surfactant component in the surfactant composition of the present invention, it has been conventionally used. Use of nonionic surfactants such as polyoxyethylene nonyl phenyl ether, polyoxyethylene dodecyl ether, ethoxylates of oxo alcohols having 12 to 15 carbon atoms, polyoxyethylene oleyl ethers, ethoxylates of mono- or distyrenated phenols, and the like. Can be.
【００１３】本発明の界面活性剤組成物中には目的に応
じ陰イオン界面活性剤又は陽イオン界面活性剤を併用す
るのが好ましい。本発明組成物中のこれらイオン性界面
活性剤の量は、重合安定性と化学的安定性の両立の観点
から、好ましくは15〜70重量％、特に好ましくは20〜50
重量％である。It is preferable to use an anionic surfactant or a cationic surfactant in the surfactant composition of the present invention according to the purpose. The amount of these ionic surfactants in the composition of the present invention is preferably from 15 to 70% by weight, particularly preferably from 20 to 50%, from the viewpoint of achieving both polymerization stability and chemical stability.
% By weight.
【００１４】本発明で用いられる陰イオン界面活性剤と
しては、直鎖アルキル硫酸エステル塩、直鎖アルキルベ
ンゼンスルホン酸塩（ＬＡＳ）、ポリオキシエチレンア
ルキルエーテル硫酸エステル塩、ポリオキシエチレンア
ルキルフェニルエーテル硫酸エステル塩等が挙げられ
る。本発明で用いられる陽イオン界面活性剤としてはア
ルキルトリメチルアンモニウム塩、アルキルピリジニウ
ム塩、アルキルベンジルジメチルアンモニウム塩等が挙
げられる。これらのイオン性界面活性剤は、水溶性に優
れた水溶液として市販されており、溶解操作は比較的容
易である。The anionic surfactant used in the present invention includes linear alkyl sulfates, linear alkyl benzene sulfonates (LAS), polyoxyethylene alkyl ether sulfates, and polyoxyethylene alkyl phenyl ether sulfates. And the like. Examples of the cationic surfactant used in the present invention include an alkyltrimethylammonium salt, an alkylpyridinium salt, and an alkylbenzyldimethylammonium salt. These ionic surfactants are commercially available as aqueous solutions having excellent water solubility, and the dissolving operation is relatively easy.
【００１５】本発明組成物の特に好ましい組成は、式
（Ｉ）の化合物が80〜50重量％、陰イオン界面活性剤が
20〜50重量％である。A particularly preferred composition of the composition according to the present invention comprises 80 to 50% by weight of the compound of the formula (I) and an anionic surfactant.
20 to 50% by weight.
【００１６】本発明の乳化重合法における本発明組成物
の使用量は、モノマーの総量に対し0.1〜10重量％が好
ましく、特に0.5〜３重量％が好ましい。The amount of the composition of the present invention used in the emulsion polymerization method of the present invention is preferably from 0.1 to 10% by weight, particularly preferably from 0.5 to 3% by weight, based on the total amount of the monomers.
【００１７】本発明の乳化重合法に使用されるモノマー
としては、スチレン、α−メチルスチレン、クロロスチ
レン等の芳香族ビニル系モノマー；アクリル酸エチル、
アクリル酸ブチル、アクリル酸２−エチルヘキシル等の
アクリル酸エステルモノマー、メタクリル酸メチル、メ
タクリル酸ブチル、メタクリル酸ドデシル等のメタクリ
ル酸エステルモノマー；塩化ビニル、臭化ビニル、塩化
ビニリデン等のハロゲン化ビニル及びハロゲン化ビニリ
デンモノマー；アクリロニトリル等のニトリル系モノマ
ー；ブタジエン、イソプレン、クロロプレン等の共役ジ
エン系モノマー等を挙げることができる。これらのモノ
マーは、単独で重合させても共重合させてもよい。また
アクリル酸、メタクリル酸、スチレンスルホン酸塩等の
水溶性モノマーや、Ｎ−メチロールアクリルアミド等の
官能性基をもつモノマーを必要により少量併用してもよ
い。モノマーの使用量は全系に対して、好ましくは30〜
70重量％、特に好ましくは40〜60重量％である。The monomers used in the emulsion polymerization method of the present invention include aromatic vinyl monomers such as styrene, α-methylstyrene and chlorostyrene; ethyl acrylate;
Acrylic ester monomers such as butyl acrylate and 2-ethylhexyl acrylate; methacrylic ester monomers such as methyl methacrylate, butyl methacrylate and dodecyl methacrylate; vinyl halides and halogens such as vinyl chloride, vinyl bromide and vinylidene chloride Vinylidene fluoride monomers; nitrile monomers such as acrylonitrile; conjugated diene monomers such as butadiene, isoprene and chloroprene. These monomers may be polymerized alone or copolymerized. In addition, a small amount of a water-soluble monomer such as acrylic acid, methacrylic acid, or styrene sulfonate, or a monomer having a functional group such as N-methylolacrylamide may be used if necessary. The amount of the monomer used is preferably 30 to
70% by weight, particularly preferably 40-60% by weight.
【００１８】本発明の乳化重合法に用いる開始剤は公知
のもので良く、K2S2O8 、(NH4)2S2O 8等の過硫酸塩、ｔ
−ブチルペルオキサイド、クメンヒドロペルオキサイ
ド、パラメンタンペルオキサイド等の有機過酸化物、ア
ゾビスイソブチロニトリル、２，２’−アゾビス（２−
アミジノプロパン）ジハイドロクロライド等のアゾ系開
始剤、さらには過酸化化合物に亜硫酸ナトリウム等の還
元剤を組合せたレドックス開始剤等が挙げられる。重合
温度は開始剤分解温度に対応して選択されるが、過硫酸
塩の場合70〜80℃が一般的である。The initiator used in the emulsion polymerization method of the present invention is known.
Is good, KTwoSTwoO8, (NHFour)TwoSTwoO 8Persulfate such as t
-Butyl peroxide, cumene hydroperoxide
Organic peroxides such as
Zobisisobutyronitrile, 2,2'-azobis (2-
Azo-based compounds such as amidinopropane) dihydrochloride
Reduction of sodium sulfite etc.
Redox initiators and the like in combination with a base agent are exemplified. polymerization
The temperature is selected according to the initiator decomposition temperature,
70-80 ° C. for salts is common.
【００１９】モノマーの添加方法は一括添加法、モノマ
ー滴下法、あるいはプレエマルション法を用いることが
できるが、急激な重合を抑制するためにモノマー滴下
法、プレエマルション法が好ましい。As the method of adding the monomer, a batch addition method, a monomer dropping method, or a pre-emulsion method can be used, but a monomer dropping method or a pre-emulsion method is preferable in order to suppress rapid polymerization.
【００２０】本発明の乳化重合法は、一括重合であって
も非イオン界面活性剤の溶解工程を短縮するのに有効で
あるが、プレエマルションを調製する工程を有する乳化
重合法に特に有効である。プレエマルションを調製する
工程を有する乳化重合法としては、 （１）開始剤を含む水相にプレエマルションの一部を添
加して、重合を開始したのち所定温度に保ちポリマー粒
子核を十分形成させたのち、あるいは重合開始後引き続
いてプレエマルションを滴下し、粒子を成長させる方法 （２）核となるシードポリマー粒子をあらかじめ水相に
所定量添加しておき、これにプレエマルションを滴下し
粒子を成長させるシード重合法 等が代表的な方法であるが、粒子成長と同時に核形成を
起こすような条件で重合する方法でも良い。The emulsion polymerization method of the present invention is effective for shortening the step of dissolving the nonionic surfactant even in batch polymerization, but is particularly effective for the emulsion polymerization method having a step of preparing a pre-emulsion. is there. The emulsion polymerization method having a step of preparing a pre-emulsion includes: (1) adding a part of the pre-emulsion to an aqueous phase containing an initiator, starting polymerization, keeping the temperature at a predetermined temperature, and sufficiently forming polymer particle nuclei. Thereafter, or after the initiation of polymerization, the pre-emulsion is dropped and the particles are grown. (2) A predetermined amount of seed polymer particles serving as a nucleus is added to the aqueous phase in advance, and the pre-emulsion is dropped to the particles to add particles. A typical method is a seed polymerization method for growing the particles, but a method of polymerizing under conditions that cause nucleation at the same time as the particle growth may be used.
【００２１】[0021]
【実施例】例中の％は特記しない限り重量％である。EXAMPLES In the examples,% is% by weight unless otherwise specified.
【００２２】実施例１〜６及び比較例１〜５ （ａ）プレエマルションの調製 (1) 200mLのビーカーに25℃のイオン交換水80ｇをと
り、下記に示す本発明に係わる非イオン界面活性剤（Ｎ
−１）〜（Ｎ−４）、その他の非イオン界面活性剤（Ｎ
−５）〜（Ｎ−８）から選ばれる非イオン界面活性剤６
ｇを60℃で溶融して添加した。これを長さ30mmの磁気攪
拌子で200回転毎分で攪拌し、非イオン界面活性剤を完
全に溶解させて水溶液を得た。この時、非イオン界面活
性剤が完全に溶解するまでの時間を測定し、表１に示し
た。Examples 1 to 6 and Comparative Examples 1 to 5 (a) Preparation of pre-emulsion (1) In a 200 mL beaker, put 80 g of ion-exchanged water at 25 ° C., and prepare the following nonionic surfactant according to the present invention. (N
-1) to (N-4) and other nonionic surfactants (N
-5) Nonionic surfactant 6 selected from (N-8)
g was melted at 60 ° C. and added. This was stirred with a magnetic stirrer having a length of 30 mm at 200 revolutions per minute to completely dissolve the nonionic surfactant to obtain an aqueous solution. At this time, the time until the nonionic surfactant was completely dissolved was measured and is shown in Table 1.
【００２３】＜非イオン界面活性剤＞ （Ｎ−１）：n−C11H23O−(EO)35−H[0023] <nonionic surfactant> (N-1): n -C 11 H 23 O- (EO) 35 -H
【００２４】[0024]
【化３】 Embedded image
【００２５】（Ｎ−３）：ダイヤドール11（１−デセン
を原料とする炭素数11のオキソアルコール、直鎖率50
％）のEO35モル付加物 （Ｎ−４）：ダイヤドール11（１−デセンを原料とする
炭素数11のオキソアルコール、直鎖率50％）のEO18モル
付加物 （Ｎ−５）：n−C12H25O−(EO)35−H （Ｎ−６）：ノニルフェノールのEO35モル付加物 （Ｎ−７）：n−C12H25O−(EO)18−H （Ｎ−８）：n−C8H17O−(EO)35−H (2) (1)で得られた非イオン界面活性剤の水溶液に、下
記に示す陰イオン界面活性剤（Ａ−１）又は（Ａ−２）
を25％水溶液として６ｇ、過硫酸カリウム0.50ｇを溶解
し、さらにイオン交換水を追加して全量112.6ｇにし
た。500mLのビーカーにアクリル酸ブチル123.75ｇ、メ
タクリル酸メチル123.75ｇ、アクリル酸2.5ｇをとりモ
ノマー混合物を調製し、これに上記の水溶液112.6ｇを
添加しホモミキサー（特殊機化工業製）にて2000回転毎
分で10分間乳化しモノマー乳化物（プレエマルション）
を調製した。得られたプレエマルションの安定性を下記
方法で評価した。結果を表１に示す。(N-3): Diadol 11 (oxo alcohol having 11 carbon atoms, starting from 1-decene, linear ratio 50
%) Of EO 35 mole adduct (N-4): Diadol 11 (oxo alcohol having 11 carbon atoms, starting from 1-decene, linear ratio 50%), EO 18 mole adduct (N-5): n- C 12 H 25 O- (EO) 35 -H (n-6): EO35 mol adduct of nonylphenol (n-7): n- C 12 H 25 O- (EO) 18 -H (n-8): to an aqueous solution of nonionic surface active agent obtained by the n-C 8 H 17 O- ( EO) 35 -H (2) (1), anionic surfactants shown below (a-1) or (A- 2)
Was dissolved as a 25% aqueous solution in an amount of 6 g and potassium persulfate in an amount of 0.50 g, and ion-exchanged water was added to make the total amount 112.6 g. In a 500 mL beaker, 123.75 g of butyl acrylate, 123.75 g of methyl methacrylate, and 2.5 g of acrylic acid were prepared to prepare a monomer mixture. To the mixture was added 112.6 g of the above aqueous solution, and a homomixer (manufactured by Tokushu Kika Kogyo) was added. Emulsified monomer for 10 minutes at every rotation (pre-emulsion)
Was prepared. The stability of the obtained pre-emulsion was evaluated by the following method. Table 1 shows the results.
【００２６】＜陰イオン界面活性剤＞ （Ａ−１）：直鎖アルキル（炭素数12）ベンゼンスルホ
ン酸ナトリウム （Ａ−２）：ポリオキシエチレン（EO平均付加モル数
３）ラウリルエーテル硫酸エステルのナトリウム塩 ＜プレエマルションの安定性試験＞プレエマルションを
100mLのガラスびん（蓋つき、内径36mm、高さ100mm）に
とり、室温で一日放置後、分層した水相の量を測定し、
水層の量から乳化物中の全部の水に対する、分層した水
相の百分率を求め、これを水分離率とした。水分離率が
少ないほどプレエマルションの安定性が良好である。<Anionic surfactant> (A-1): linear alkyl (C12) sodium benzenesulfonate (A-2): polyoxyethylene (average number of moles of EO added: 3) lauryl ether sulfate Sodium salt <Pre-emulsion stability test>
Take in a 100 mL glass bottle (with lid, inner diameter 36 mm, height 100 mm), leave it at room temperature for one day, measure the amount of separated aqueous phase,
From the amount of the aqueous layer, the percentage of the separated aqueous phase with respect to all the water in the emulsion was determined, and this was defined as the water separation rate. The smaller the water separation ratio, the better the stability of the pre-emulsion.
【００２７】（ｂ）乳化重合 容量１Ｌのセパラブルフラスコにイオン交換水138ｇ及
び（ａ）(2)で得られたプレエマルション39ｇを仕込
み、窒素気流中で攪拌しながら水浴で20分かけて80℃に
昇温した。昇温後残りのプレエマルション316ｇを２時
間かけて滴下した。この間フラスコ内の温度は80℃に保
持した。滴下終了後80℃でさらに３時間保って重合を完
了させ、室温まで冷却してポリマーエマルションを得
た。この時の重合安定性及び得られたエマルションの性
能を下記方法で評価した。結果を表１に示す。(B) Emulsion polymerization 138 g of ion-exchanged water and 39 g of the pre-emulsion obtained in (a) (2) were charged into a separable flask having a capacity of 1 L, and stirred in a water bath for 20 minutes while stirring in a nitrogen stream. The temperature was raised to ° C. After the temperature was raised, 316 g of the remaining pre-emulsion was added dropwise over 2 hours. During this time, the temperature in the flask was kept at 80 ° C. After completion of the dropwise addition, the mixture was kept at 80 ° C. for 3 hours to complete the polymerization, and cooled to room temperature to obtain a polymer emulsion. At this time, the polymerization stability and the performance of the obtained emulsion were evaluated by the following methods. Table 1 shows the results.
【００２８】＜重合安定性＞得られたポリマーエマルシ
ョンを200メッシュのステンレス製金網で濾過し、重合
後の反応器器壁や攪拌はね等に付着した凝集物も集めて
同様に濾過した。水洗後26.6kPa、105℃で２時間乾燥・
秤量して、凝集物量を求め、使用したモノマーの総量に
対する凝集物の重量％で重合安定性を表示した。<Polymerization Stability> The obtained polymer emulsion was filtered through a 200-mesh stainless steel wire gauze. Aggregates adhering to the reactor wall and the stirring spring after polymerization were collected and filtered in the same manner. After washing with water, dry at 26.6kPa and 105 ℃ for 2 hours.
The weight of the aggregate was determined by weighing, and the polymerization stability was indicated by the weight% of the aggregate relative to the total amount of the monomers used.
【００２９】＜ポリマーエマルションの性能評価＞ ・機械的安定性 上記の濾過したポリマーエマルションを25％アンモニア
水で中和しpH8.5に調節して、中和後のポリマーエマル
ション50ｇを使ってマロン安定試験機で機械的安定性を
測定した（条件：10kgf、1000回転毎分、５分間）。試
験で生成した凝集物を200メッシュのステンレス製金網
で濾過し、濾過残渣を水洗後に26.6kPa、105℃で２時間
乾燥・秤量し、ポリマーに対する凝集物の重量％で機械
的安定性を表示した。 ・平均粒径 コールター社製の動的光散乱法による粒径測定装置Ｎ−
４ＳＤを使用して、ポリマーエマルション粒子の平均粒
径（nm）を測定した。 ・化学的安定性 ポリマーエマルションをイオン交換水でポリマー濃度３
％に希釈し、１Ｍの塩化カルシウム水溶液を用いて滴定
することにより、凝集物が生じ始める濃度（mM）を求め
これを化学的安定性とした。<Performance evaluation of polymer emulsion>-Mechanical stability The filtered polymer emulsion was neutralized with 25% aqueous ammonia and adjusted to pH 8.5, and malon was stabilized using 50 g of the neutralized polymer emulsion. The mechanical stability was measured with a testing machine (conditions: 10 kgf, 1000 rotations per minute, 5 minutes). The aggregate generated in the test was filtered through a 200-mesh stainless steel wire net, and the filtration residue was washed with water, dried and weighed at 26.6 kPa and 105 ° C. for 2 hours, and the mechanical stability was indicated by the weight% of the aggregate relative to the polymer. .・ Average particle size Particle size measuring device N- by Coulter Co., Ltd. by dynamic light scattering method
The average particle size (nm) of the polymer emulsion particles was measured using 4SD.・ Chemical stability Polymer emulsion is polymerized with ion-exchanged water at a polymer concentration of
%, And titrated with a 1 M aqueous solution of calcium chloride to determine the concentration (mM) at which aggregates begin to form, and this was taken as the chemical stability.
【００３０】[0030]
【表１】 [Table 1]
【００３１】実施例７〜１０及び比較例６〜７ 表２に示す非イオン界面活性剤及び陰イオン界面活性剤
を用い、非イオン界面活性剤の使用量を５ｇ、25％陰イ
オン界面活性剤の使用量を10ｇとし、モノマー混合物の
組成をアクリル酸ブチル121.25ｇ、スチレン121.25ｇ、
アクリル酸7.5ｇとする以外は実施例１〜６及び比較例
１〜５と同様にして乳化重合を行い、同様に性能を評価
した。結果を表２に示す。Examples 7 to 10 and Comparative Examples 6 to 7 Using a nonionic surfactant and an anionic surfactant shown in Table 2, the amount of the nonionic surfactant used was 5 g, and a 25% anionic surfactant was used. The amount of used is 10 g, the composition of the monomer mixture is 121.25 g of butyl acrylate, 121.25 g of styrene,
Emulsion polymerization was performed in the same manner as in Examples 1 to 6 and Comparative Examples 1 to 5 except that the amount of acrylic acid was changed to 7.5 g, and the performance was similarly evaluated. Table 2 shows the results.
【００３２】[0032]
【表２】 [Table 2]
【００３３】[0033]
【発明の効果】本発明の界面活性剤組成物を乳化重合に
用いると、水への溶解時間が短く加温などの操作が不要
であり、モノマー乳化性に優れ、重合安定性がよく、機
械的安定性、化学的安定性に優れたポリマーエマルショ
ンを得ることができる。When the surfactant composition of the present invention is used for emulsion polymerization, the dissolving time in water is short, no operation such as heating is required, monomer emulsification is excellent, polymerization stability is good, and mechanical Polymer emulsion having excellent chemical stability and chemical stability can be obtained.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 沢田 広樹 和歌山県和歌山市湊1334 花王株式会社研 究所内 Ｆターム(参考） 4D077 AA05 AB06 AB14 AC01 BA03 BA07 BA15 DC08Z DC14Z DD08Y DD32Y DE02Y DE07Y DE08Y 4J011 KA10 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Hiroki Sawada 1334 Minato, Wakayama-shi, Wakayama Prefecture F-term (reference) 4D077 AA05 AB06 AB14 AC01 BA03 BA07 BA15 DC08Z DC14Z DD08Y DD32Y DE02Y DE07Y DE08Y 4J011 KA10
Claims (3)
の含有量が、非イオン界面活性剤成分の50重量％以上で
ある乳化重合用界面活性剤組成物。 【化１】 （式中、x，yはそれぞれ０以上の整数で、x＋y＝８であ
る。EOはオキシエチレン基を示し、nはオキシエチレン
基の平均付加モル数を示す５〜100の数である。）1. A surfactant composition for emulsion polymerization, comprising a compound represented by the formula (I), the content of which is at least 50% by weight of the nonionic surfactant component. Embedded image (In the formula, x and y are each an integer of 0 or more, and x + y = 8. EO represents an oxyethylene group, and n is a number of 5 to 100 that represents the average number of moles of the oxyethylene group added.)
成物を用いるビニル系モノマーの乳化重合法。2. A method for emulsion polymerization of a vinyl monomer using the surfactant composition for emulsion polymerization according to claim 1.
る請求項２記載の乳化重合法。3. The emulsion polymerization method according to claim 2, further comprising a step of preparing a pre-emulsion.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091917A (en) * | 2005-09-29 | 2007-04-12 | Dainippon Ink & Chem Inc | Method for producing resin emulsion for paper processing |
| JP2015521675A (en) * | 2012-06-25 | 2015-07-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Emulsion polymerization method |
-
2000
- 2000-06-15 JP JP2000179491A patent/JP2001354709A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007091917A (en) * | 2005-09-29 | 2007-04-12 | Dainippon Ink & Chem Inc | Method for producing resin emulsion for paper processing |
| JP2015521675A (en) * | 2012-06-25 | 2015-07-30 | ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ | Emulsion polymerization method |
| KR102060948B1 (en) | 2012-06-25 | 2019-12-31 | 바스프 에스이 | Process for emulsion polymerization |
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